CC BY
22
UDC 678.046.39:678.7-1
M. A. Mikitaev, G. V. Kozlov, A. K. Mikitaev, G. E. Zaikov
THE DEPENDENCE OF MELT VISCOSITY OF POLYMER NANOCOMPOSITES ON TYPE OF CARBON NANOTUBES FRACTAL STRUCTURES
Keywords: nanocomposite, blend, carbon nanotubes, melt, viscosity, fractal.
As it is known, any real fractal object can be simulated as a bulk or surface fractal. In the first case the structure fractality is extended to the entire volume of the object and in the second one - to its surface. For nanocomposites, the matrix of which makes up polymer blend poly(ethylene terephthalate)/poly(butylene terephthalate), the fractal dimensions of both structure and surface of ring-like formations of nanofiller (multiwalled CNT) were calculated. It has been found out that in case of their notion as bulk fractals, i.e. matrix polymer penetration in ring-like formations internal regions, the strong enhancement of the nanocomposites melt viscosity is observed and in case of surface fractals this parameter is independent on nanofiller contents.
Ключевые слова: нанокомпозит, смесь, углеродные нанотрубки, расплав, вязкость, фрактал.
Как известно, любой реальный фрактальный объект может быть смоделирован как массовый или поверхностный фрактал. В первом случае, фрактальная структура распространяется на весь объем объекта, а во втором - на его поверхность. Для нанокомпозитов, матрицу которых составляет полимерная смесь поли (этилентерефталат)/поли (бутилентерефталат), рассчитаны фрактальные размерности структуры и поверхности кольцевых образований нанонаполнителя (многослойных CNT). Обнаружено, что в случае их представления в виде объемных фракталов, т.е. матричного проникновения полимера в кольцевые образования внутренних областей, наблюдается сильное повышение вязкости расплава нанокомпозитов, а в случае поверхностных фракталов этот параметр не зависит от содержания нанонаполнителя.
Introduction
Inorganic nanofillers of different types usage for polymer nanocomposites receiving acquires at present wide spreading [1]. However, the indicated nanomaterials melt properties are not studied enough completely. As a rule, when nanofillers application is considered, then the compromise is achieved between improvement of mechanical properties in solid-phase state, enhancement of melt viscosity at processing, nanofillers dispersion problem and process economic characteristics. Proceeding from this, the relation between nanofiller concentration and geometry and nanocomposites melt properties is an important aspect of polymer nanocomposites study.
It has been shown earlier [2], that nanocomposites polypropylene/carbon nanotubes melt viscosity is not changed practically at nanofiller contents variation within the range of 0.25-3.0 mass. %. However, in work [3] the sharp (in 3.5 times) reduction of melt viscosity of nanocomposites on the basis of blend poly(ethylene terephthalate)-poly(butylene terephthalate), filled with multiwalled carbon nanotubes (PET-PBT/MWCT) was found in comparison with the initial matrix polymer blend at MWCT content of 0.45 mass. % only. Therefore, the present paper purpose is this effect study with the fractal analysis notions using.
Experimental
The polymers industrial sorts were used: PET was supplied by firm GE Plastics and PBT of mark S6110SF NC010, supplied by firm DuPont TM Crastin. As nanofiller MWCT were used with external diameter ranging between 10-30 nm and length of 1.5 mcm of firm Sun Nano production [3].
The blends PET/PBT, having optimal PET content of 20 mass. %, were blended with MWCT at
nanofiller contents of 0.15-0.45 % by weight in melt with usage of twin screw extruder (Bersfort FRG Germany) at temperature of 493 K and screw rotation speed of 150 rpm. After receiving, the extrudate was cooled in water and pelletized. The testing samples were prepared from these pellets using injection molding machine (Windsor, India) at temperature range of 523558 K [3].
The uniaxial tension mechanical tests were performed according to ASTM D628 on testing apparate of model AG Rnisd MC of form Shimadzu Autograph at temperature of 296 K and the cross head speed of 50 mm/min, that corresponds to the strain rate of 1.67x10-2 s-1. Melt flow index (MFI) was measured according to ASTM D1238 [3].
Results and Discussion
As it was noted above, for nanocomposites PET-PBT/MWCT very strong increase of viscosity (MFI reduction) was observed in comparison with matrix polymer blend [3]. This effect was fixed at very small MWCT volume content <pn, which can be determined as follows [1]:
(1>
Pn
where Wn is nanofiller mass content, pn is its density, which for nanoparticles is determined according to the equation [1]:
Pn= 188(Z?mwct )1/3, kg/m3, (2)
where Dmwct is MWCT diameter, which is given in nm.
According to the continuum conception [4] the relation between composites melt viscosity matrix polymer melt viscosity -q0 and <pn can be obtained in the form of two simple relationships:
L Lo
L _ 2-5Рп Lo
Л+ рп ,
1-Рл
(3)
(4)
The equations (3) and (4) give the greatest q increasing in comparison with q0 on 0.8-2.0 %, that does not correspond to experimentally observed q growth in 3.5 times.
The authors [2] proposed the fractal model of polymer nanocomposites melt viscosity change, the main equation of which is the following one:
L Lo1
2-d,
(5)
where l is flow characteristic linear scale, df is fractal dimension.
Since carbon nanotubes, possessing anisotropy high degree and low transverse stiffness, are formed in polymer matrix ring-like structures with radius RCNT [5, 6], then this dimensional parameter was accepted as l, which can be determined with the aid of the equation [7]:
Рп =■
жЬ
■mwct'mwct
(6)
(cnt )3
where LMWCT and tmwCT are length and radius of carbon nanotubes, respectively.
Since contact polymer matrix-nanofiller is
realized through the ring-like structures, then as df the
authors [2] have accepted these structures surface dimension durf, which is determined according to the following technique. First the specific surface Su was estimated according to the equation [1]:
3
s,, _■
(7)
PCNT^CNT
where pCNT is the density of MWCT rang-like structures, which is accepted equal to pn.
Then the value dsurf can be determined with the aid of the following formula [1]:
Su = 410(Rcnt , (8)
where d is dimension of Euclidean space, in which a fractal is considered (it is obvious, that in our case d=3).
In Fig. 1 the dependence of MFI on MWCT volume contents <p„ is adduced (the curve 1) for the considered nanocomposites, where the value MFI is determined as follows [8]:
MFI = —, g/10 min. (9)
q
As it follows from the data of Fig. 1, at the condition df =dsurf MFI value is practically constant, that does not correspond to the experimental results [3].
As it is known [9], fractals can be divided into two categories: bulk and surface ones. In the first case fractality property is extended to the object volume and in the second one - to its surface only. For the bulk fractals their dimension , i.e. dimension of
MWCT ring-like structures, is determined with the aid of the relationship [10]:
4c0kT
HdC
AldC
, . . (10)
3qM0
where c0 is nanoparticles initial concentration, which is accepted equal to <p„, k is Boltzmann constant, T and t are temperature and duration of processing, respectively, q is melt viscosity, M0 is mass of separate nanoparticle.
Fig. 1 - The dependence of melt flow index MFI on nanofiller volume contents <n for nanocomposites PET-PBT/MWCT. 1, 2 - the theoretical calculation according to the relationship (5) for cases of surface (1) and bulk (2) fractals, 3 - experimental data
Since the parameters k, T, t and M0 are constant, and q~MFI-1, then the relationship (10) can be simplified as follows:
WCNT
/?CNT ~<P„* MFI. (11)
In Fig. 1 the dependence of MFI(<p„) for the considered nanocomposites is also adduced, which is calculated according to the relationship (5) at the
condition , i.e. at simulation of MWCT ring-
like structures as bulk fractals. In this case the good correspondence of theory and experiment is obtained.
As it is known [11], for bulk fractals penetration of polymer matrix macromolecules into their internal regions is typical. The number of macromolecules n, penetrating into these regions, is given by the following relationship [11]:
n ~ rCNt , (12)
where Af is the fractal dimension of polymer melt macromolecular coil, determined as follows [12]: A f=(d-1)(1 + v), (13)
where v is Poisson's ratio, estimated according to the mechanical tests results with the aid of the equation [13]:
_ 1- 2v , (14)
E 6(1 + v)'
where ct7 and E are yield stress and elastic modulus, respectively.
In Fig. 2 the dependence of MFI(n) for the considered nanocomposites is adduced. As one can see, MFI reduction (melt viscosity growth) at n decreasing is
observed. At n^0 MFI«0 and the change of MWCT ring-like structures type from bulk fractal to surface one occurs.
Fig. 2 - The dependence of melt flow index MFI on polymer matrix macromolecules number n, penetrating in MWCT ring-like structures internal regions, for nanocomposites PET-PBT/MWCT
Conclusions
Thus, the present work results have shown that the dependence of melt viscosity of nanocomposites polymer/carbon nanotubes on nanofiller contents is defined by fractal structures type, which is formed by the nanofiller. In case of surface fractals very weak dependence of melt viscosity on carbon nanotubes contents is observed and in case of bulk fractals - its essential (in several times) enhancement. The absence of polymer matrix macromolecules penetration in carbon nanotubes ring-like structures internal regions defines the structures transition from bulk fractals to surface ones.
Work is performed within the complex project on creation of hi-tech production with the participation of the Russian higher educational institution, the Contract of JSC "Tanneta" with the Ministry of Education and Science of the Russian Federation of February 12, 2013 No. 02.G25.31.0008 (Resolution of the Government of the Russian Federation No. 218).
References
1. Mikitaev A.K., Kozlov G.V., Zaikov G.E., Polymer Nanocomposites: Variety of Structural Forms and Applications, Nova Science Publishers, Inc., New York, 2008, 319 p.
2. G.V. Kozlov, Z.M. Zhirikova, V.Z. Aloev, G.E. Zaikov Polymer Research J., 2012, Vol. 6, no.3, p. 267-273.
3. P.R. Rajakumar, R. Nanthini Int. J. Adv. Chem., 2013, Vol. 1, no. 2, p. 39-42.
4. N.J. Mills J. Appl. Polymer Sci., 1971, Vol. 15, no. 11, p. 2791-2805.
5. D.W. Schaefer, R.S. Justice Macromolecules, 2007, Vol. 40, no. 24, p. 8501-8517.
6. Yu.G. Yanovsky, G.V. Kozlov, Z.M. Zhirikova, V.Z. Aloev, Yu.N. Karnet Int. J. Nanomechanics Sci. Techn., 2012, Vol. 3, no. 2, p. 99-124.
7. B. Bridge J. Mater. Sci. Lett., 1989, Vol. 8, no. 2, p. 102103.
8. Kalinchev E.L., Sakovtseva M.B., Properties and Processing of Thermoplasts, Khimiya, Leningrad, 1983, 288 p.
9. Feder E., Fractals, Plenum Press, New York, 1989, 256 p.
10. D.A. Weitz, J.S. Huang, M.Y. Lin, J. Sung Phys. Rev. Lett., 1984, Vol. 53, no. 17, p. 1657-1660.
11. Kozlov G.V., Dolbin I.V., Zaikov G.E. Fractal Physical Chemistry of Polymer Solutions and Melts, Apple Academic Press, Toronto, New Jersey, 2014, 316 p.
12. Balankin A.S. Synergetics of Deformable Body, Publishers of Ministry Defence SSSR, Moscow, 1991, 404 p.
13. Kozlov G.V., Sanditov D.S. Anharmonic Effects and Physical-Mechanical Properties of Polymers, Nauka, Novosibirsk, 1994, 261 p.
© M. A. Mikitaev - Ph.D., Kh.M. Berbekov Kabardino-Balkarian State University, Nal'chik, Russia, G. V. Kozlov - Senior Researcher, Kh.M. Berbekov Kabardino-Balkarian State University, Nal'chik, Russia, A. K. Mikitaev - Doctor of Chemistry, Full Professor of Organic Chemistry and Macromolecular Compounds Department, Kh.M. Berbekov Kabardino-Balkarian State University, Nal'chik, Russia, G. E. Zaikov - Doctor of Chemistry, Full Professor, Plastics Technology Department, Kazan National Research Technological University, Kazan, Russia, [email protected].
© М. А. Микитаев - канд. хим. наук, Кабардино-Балкарский государственный университет им. Х.М. Бербекова, Нальчик, Россия, Г. В. Козлов - старший научный сотрудник, Кабардино-Балкарский государственный университет им. Х.М. Бербекова, Нальчик, Россия, А. К. Микитаев - д-р хим. наук, профессор кафедры Органической химии и высокомолекулярных соединений, Кабардино-Балкарский государственный университет им. Х.М. Бербекова, Нальчик, Россия, Г. Е. Заиков - д-р хим. наук, проф. каф. технологии пластических масс, Казанский национальный исследовательский технологический университет, Казань, Россия, [email protected].
